Process for hydroxylation of ethylenically unsaturated compounds



Patented June 6, 1950' PROCESS FOR HYDROXYLATION F ETHYL- ENICALLY UN SATUBATED COMPOUNDS Walter A. Raczynski, Wilmington, Del., assignor to Hercules Powder Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application September 30, 1948, Serial No. 52,135

18 Claims. (Cl. 260-406) This invention relates to a process for the hydroxylation of ethylenically unsaturated fatty acids and derivatives thereof. More particularly, it relates to a process for the hydroxylation of such compounds to provide hydroxylated derivatives which may be glycols or compounds having more than two hydroxyl groups per molecule depending upon the number of ethylenic linkages and the position thereof in the starting material.

The prior art discloses various ways for converting oleflnes and oleilne compounds to hydroxylated compounds, for example, the addition of the elements of hypohalous acid followed by hydrolysis to yield hydroxylated compounds. This process sufiers from the disadvantage that a considerable amount of rather nonreactive and undesirable diahalide compounds are obtained, also that during hydrolysis substantial amount of undesirable byproducts such as olefine oxides or unsaturated alcohols are formed. Another process is that of U. 8. Patent 2,033,538 which describes the oxidation of oleic acid by means of hot hypochlorite solutions and nickel salts. This process, however, is of little commercial interest due to the undesirable polyhalogenated acids, as well as cleavage products, formed as byproducts. The air oxidation 01 oleic acid and other oleflne compounds has been shown to yield hydroxylated compounds, but the yields are so low due to polymerization reactions tthat the process is of little value. Hydroxylation of olefines and oleflne compounds by means of alkaline permanganate solutions has also been tried. This process is disadvantageous due to the large volumes oi liquid that must be handled and due to formation of hydrated manganese dioxide which occludes the products and which must be removed to enable isolation of the products.

Finally, it is known to hydroxylate oleic acid and other olefine acids using a slurry of concentrated sulfuric acid and ammonium persulfate. The great amount of heat involved in this process makes the reaction very diificult to control and to prevent carbonization of the reactants and products. The reaction mixture also sets to a. viscous solid during the reaction which makes it very impractical on a large scale. Considerable suliation, and probably. sulfonation, occurs during the process, even when carefully controlled with respect to temperature, order and rate of addition of reactants, such that emulsiflcation of the mixture occurs on further prochydroxylated product are obtained. Migration of the double bonds of the reactants also occurs when this process is used, this action resulting in a complex mixture rather than a relatively pure hydroxylated compound. The disadvantages of this process are so great that it is doubtful that it couldoperate on a semi-plant scale let alone on a large scale.

In accordance with this invention, there has been found a process for the hydroxylation of ethylenically unsaturated fatty acids and derivatives thereof which provides an unusually high yield of hydroxylated product and which is not subject to the many disadvantages hereinabove noted in the priorart processes. This process comprises reacting in liquid phase said fatty acid or derivative thereof with an inorganic persuliate in-the presence of a saturated monocarboxylic acid or from 1 to 9, carbon atoms until substantial hydroxylation of the fatty acid or derivative has occurred. It is preferred, although not essential, thatthe reaction be carried out in the presence of a mineral acid having a dissociation constant for the first hydrogen at 25 C. above 1.86x 0-. Furthermore, it is preierred, although not essential, that the reaction be carried out in an aqueous medium. The product formed as a result of" the above-described process is in almost every instance a hydroxyacylate, the particular hydroxy-acylate depending upon the particular saturated monocarboxylic acid employed. The acylate group, or groups as the case may be, may be hydrolyzed to a hydroxyl group by procedures well known to the art.

Having now described the invention broadly, the following representative specific examples are given to illustrate the invention:

Example I One hundred and forty-one parts (0.5 mol) of a commercial oleic acid containing 79% oleic acid, 300 parts (5.0 mols) of glacial acetic acid, and 141 parts (0.5 mol) of ammonium persulfate dissolved in 150 parts of water were added to a 2-liter flask equipped with. a stirrer, condenser, dropping funnel, and thermometer. The mixture was heated to 20 C. and 58 parts (0.592 mol) of concentrated sulfuric acid were added dropwise over a period of 27 minutes with efllcient stirring. The sulfuric acid'employed was aqueous 95% acid. The temperature of the reaction mixture was then raised to 40 C. and held there for 2 hours. The temperaturevwas then raised to essing and low yields of the desired unsulfated 5| C. over a period of 50 minutes and main- Acid number 1'72 Hydroxyl value (by acetylation) -per cent 10.5 Iodine number 2 The.filtrate was evaporated at an absolute pressure of 20 mm. to remove solvent and 77 parts of a brown oily solid was obtained having the following characteristics:

Acid number 1'18 Hydroxyl value -.......per cent-.. 6.3 Iodine number 9.0

Example II One hundred and forty-one parts (0.5 mol) of commercial oleic acid containing 83% oleic acid, 1200 parts (20.0 mois) of glacial acetic acid, and 141 parts (0.5 mol) of ammonium persuifate, dissolved in 660 parts of water, were mixed at 20 C. in a 2-liter flask equipped with stirrer, refiux condenser, thermometer, and dropping funnel. Fifty-eight parts (0.592 mol) of concentrated sulfuric acid were added dropwise over a period of seven minutes with efilcient stirring, and the temperature was then raised to 70 C. in one-half hour and held there for one hour. The reaction mixture was processed as in Example I to yield 74 parts of crystalline solid. This represented a yield of 9,10-dihydroxystearic acid of 56.4% of theory. The product had the following characteristics:

Acid number 176 Evdroxyi value per cent 10.6

Acid number Hydroxyl value per cent 8.8 Iodine number Example III One hundred and forty-one parts (0.5 mol) of oleic acid containing 82% oleic acid, 300 parts (5.0 mois) of acetic acid, and 135 parts (0.5 mol) of potassium persulfate, suspended in 150 parts of water, were added to a 2-liter flask equipped with a reflux condenser, thermometer, stirrer, and dropping funnel. Fifty-eight parts (0.592 mol) of concentrated sulfuric acid were added dropwise with efilcient stirring at C. and then the mixture was heated at 40 C. for four hours. The temperature was raised to 70 C. over a period of one hour and the reaction mixture then cooled to room temperature. Processing of the reaction mixture as in Example I yielded 61 parts of crystalline 9,10-dihydroxystearic acid, representing a yield of 46.5% of theory. The product.

The filtrate treated as in Example I yielded 81 parts of an oily solid which had the following characteristics:

Acid number 183 Hydroxyl value per cent 4.3

Iodine number 28 Example IV One hundred and forty-one parts (0.5 mol) of commercial oleic acid containing 79% oleic acid and 300 parts (5.0 mois) of glacial acetic acid were mixed at 20 C. A solution of 141 parts (0.5 mol) of ammonium persulfate in 230 parts of water containing 58 parts (0.592 mol) of concentrated sulfuric acid was slowly added to the oleic acid-acetic acid solution with stirring. The mixture was heated to 40 C. and held at that temperature for 3 hours. Thereafter, the temperature of the mixture was raised to 70 C. over a period of one hour, and the mixture was held at that temperature for an additional hour. The resulting reaction mixture was processed as in Example I to yield 61 parts of crystalline solid which represented a yield of 48.8% of theory. The product had the following characteristics:

Acid number 172 Hydroxyl value -per cent 9.8 Iodine number 2 The benzene filtrate was treated in accordance with Example I to provide 89 parts of an oil having the following characteristics:

Acid number Hydroxyl value per cent..- 5.7 Iodine number 20 The process of the present invention is applicable to a large number of ethylenically unsaturated compounds. In general, there may be employed any of the ethylenically unsaturated fatty acids, any of the ethylenically unsaturated fatty alcohols, any monohydric or polyhydric alcohol esters of the aforesaid unsaturated'fatty acids, or any monocarboxylic or polycarboxylic acid esters of the aforesaid unsaturated fatty alcohols. The preferred compounds are the ethylenically unsaturated fatty acids or alcohols of comparatively high molecular weight; 1. e., those of 10 carbon atoms or higher, and the aforementioned derivatives thereof. 1

Accordingly, there may be employed monounsaturated fatty acids as acrylic, crotonic, isocrotonic, vinylacetic, methylacrylic, tiglic, angelic, senecioic, teracrylic, undecylenic, hypogeic, lauroleic, myristoleic, palmitoleic, oleic, gadoleic, erucic, elaidic, brassidic, behenic, nervonic, etc. acids; (ii-unsaturated fatty acids such as (2,4-pentadienoic), (2,4-hexadienoic), (3,7-methyl-2,6-octadienoic) linoleic, etc.; tri-unsaturated fatty acids such as (3,7-methyl-2,4,6-octatrienoic), linolenic, elaeostearic, licanic, etc. acids; fatty acids of still higher unsaturation such as clupanodonic, arachidonic, etc. acids. As evidenced by the fact that certain of the named acids possess conjugated ethylenic unsaturation, any fatty acids possessing this type of unsaturation may be employed.

As stated previously, ethylenically unsaturated fatty alcohols may be employed as starting material. Unsaturated alcohols can be prepared from ethylenically unsaturated fatty acids by procedures well known to the art, for example, by sodium reduction of alcoholic solutions of esters of the fatty acids. As exemplary of the unsaturated alcohols which may be employed, there may be mentioned allyl alcohol, methylvinylcarbinol, crotyl alcohol, allylcarbinol, pentn-1-ol-5, oleyl alcohol, etc.

Substitution products of the above-mentioned unsaturated fatty acids or alcohols, i. e., compounds .wherein one or more ofthe hydrozens attached to the carbon chain have been substituted, may, if desired, be used as starting materials in carrying out the process of this invention. For example, amino-, halo-, hydroxyl-, cyano-, imino-, nitro-, etc. substituted unsaturated fatty acids or alcohols may be employed. It is necessary in such substitution products, however, that there be at least one -CH=CH-- group present, It will be understood that, in the use of substitution products having substituent groups which are attacked by the reagents employed in accordance with the invention, the substituent group can be protected in accordance with methods wellknown to the art, prior to hydroxylation of the compound, and the substituent group restored after hydroxylation has been completed. For example, in the case of an amine starting material,

it may be first reacted with benzoyl chloride to form an amide and the amide hydrolyzed back to an amine after the intermediate hydroxylation reaction.

As exemplary of the esters of the aforementioned ethylenic unsaturated fatty acids which may be employed in accordance with this invention there may be mentioned monohydric alcohol esters such as the methyl, ethyl, propyl, butyl, amyl, hexyl, etc. esters; polyhydric alcohol esters such as the ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerol, erythritol, pentaerythritol, sorbitol, mannitol, etc, esters. Mixed esters of polyhydric alcohols may be employed if at least one of the acyl radicals thereof is ethylenically unsaturated. Many of the naturally occurring fats and oils contain sub stantial proportions of glycerides or mixed glycerides which contain ethylenically unsaturated acyl groups. These fats and oils are important raw materials for use in accordance with this invention due to their availability commercially. As representatives of such fats and oils, there may be mentioned castor, corn, cottonseed, hempseed, kapok, linseed, menhaden, mustard, neats-foot, oiticica, olive, palm, peanut, perilla, poppyseed, saiilower, soybean, sunflower, teaseed, tung, etc. oils.

As stated previously, esters of the aforementioned ethylenically unsaturated fatty alcohols may be hydroxylated using the process described herein. Thus, esters of such fatty alcohols with monocarboxylic acids such as formic, acetic, propionic, butyric, valeric, caproic, etc. acids and esters of such fatty alcohols with polycarboxylic acids such as oxalic, malonic, methylmalonic, succinic, methylsuccinic, adipic, pimelic, suberic, azelaic, sebacic, etc. acids, may be employed.

The compound used as starting material may have a -CH=CH group in a terminal or nonterminal position in the molecule. Compounds containing a single CH=CH group provide e.,fi-glYCOlS. Compounds containing two --CH=CH groups in conjugated relationship also provide diols which, however, do not necessarily have the hydroxyl groups on adjacent carbon atoms, 1. e., they are not necessarily 41,,8- glycols. Compounds having more than one --CH=CH- group, not in conjugated relatiomship, usually provide compounds having more than two hydroxyl groups per molecule as for example tetrols, etc.

In general, any saturated monocarboxylic acid of from 1 to 9 carbon atoms may be employed in carrying out the process of the invention, as for example, formic, acetic, propionic, butyric, etc. acids. Of these, the acids having from 1 to 4 carbon atoms are preferred with acetic acid being the most important both from the standpoint of performance as well as for economic reasons. The saturated monocarboxylic acid should be employed in the amount of at least one mol per mol of the unsaturated compound being hydroxylated, and it is preferred to employ from 4 to 60 mols of saturated monocarboxylic acid per mol of the unsaturated compound.

Several types of persulfates have been illustrated in the examples. However, any inorganic persulfate may be employed if desired. For example, persulfuric acid, amonium, sodium, potassium, lithium, rubidium, caesium, copper, calcium, strontium, barium, etc., persulfates may be employed. Of these, the ammonium salt is preferred, followed by the potassium and sodium salts in order of importance.

The persulfate should always be employed in the amount of at least one mol per mol of the unsaturated compound being hydroxylated, otherwise there will not be sufficient of this reagent to effect the hydroxylation of all the unsaturated compound employed. An excess of the persul fate may be employed, however, there is little advantage to be gained in employing an excess of this reagent unless the reaction is carried out under conditions whereby there is loss of active oxygen, as for example, operating at comparatively high temperatures. It will be understood that the above statements apply particularly with respect to the hydroxylation of unsaturated compounds having a single --CH=CH- group or two -CH=CH- groups in conjugated relationship. Such compounds, as hereinbefore mentioned, provide diols. Where unsaturated compounds having more than one -CH=CH group present in nonconjugated relationship are employed, and where it is desired to hydroxylate more than one ofthe -CH=CH- groups, more than one mol of persulfate should be employed per mol of unsaturated compound. Thus for example, if it be desired to make a tetrol from linoleic acid, substantially two mols of persulfate should be employed per mol of linoleic acid, etc.

In place of sulfuric acid shown in the examples, I may employ any mineral acid having a dissociation constant for the first hydrogen ion at 25 C. above 1.86 10- For example, hydrochloric acid, nitric acid, hydrobromic acid, hydriodtc acid, phosphoric acid, perchloric acid, etc. may be used. Sulfuric acid is the preferred mineral acid. It is convenient to employ these acids in the form of concentrated aqueous solutions of the concentrations supplied commercially. However, various concentrations may be employed. It will be understood that monobasic as well as polybasic mineral acids may be employed and that reference to the first hydrogen ion in the foregoing limitation should not be construed as limiting the acids to. polybasic acids.

It is not essential that a mineral acid be employed in effecting hydroxylation of an unsaturated compound in accordance with this invention, although it is much preferred to employ such an acid. It is accordingly preferred to employ at least one chemical equivalent of the mineral acid per chemical equivalent of the persulfate, one chemical equivalent of persulfate being considered to be one-half mol thereof for this 7 purpose. .From one to two chemical equivalents of mineral acid per chemical equivalent of persulfate have been found to be adequate for practical operation, although amounts of mineral acid in excess thereof may be employed if desired.

In all of the examples, some water was present in the reaction mixture, it being introduced in the solution or suspension of the persulfate. It can be introduced in other ways. However, the use of water is not absolutely necessary; and hydroxylation of the unsaturated compounds hereinabove mentioned may be effected without any water present. The introduction of some water into the reaction mixture is preferred. however. When used, the water is preferably employed in the amount of from 100% to 500% by weight of the unsaturated compound being hydroxylated.

Any'order of mixing the reactants may be employed successfully in carrying out the hydroxylation reaction described herein. However, the preferred method is to mix the unsaturated compound, the saturated monocarboxylic acid and the inorganic persulfate (in aqueous solution or suspension if desired) together and thereafter to add the mineral acid slowly to the mixture. If desired, the unsaturated compound and the saturated monocarboxylic acid may first be admixed and an aqueous solution or suspension of the persulfate acidified with the mineral acid added slowly thereto as illustrated by Example IV. Furthermore, the unsaturated compound may be added slowly to an admixture of the mineral acid, the persulfate and the saturated acid. It will be obvious that the temperature of reaction employed will depend to a large extent on the particular unsaturated compound being hydroxylated. The preferred reaction temperatures are from about 10 C. to about 65 C. It should be understood, however, that hydroxylation of unsaturated compounds in accordance with the process described herein can be effected at temperatures without this range and that the invention in its broadest aspect is not limited to operation within the disclosed range.

The hydroxylated compounds prepared in accordance with this invention are very useful in the chemical arts. They constitute important intermediates which upon esterification yield desirable plasticizers, detergents and resins.

The process of this invention is extremely advantageous in that substantially improved yields are obtained as compared with prior art processes. The disadvantages of the prior art processes, hereinbefore referred to, are largely overcome. The amount and number of byproducts obtained are minimized. In this respect, very little sulfa tion or sulfonation (when sulfuric acid is used) of the unsaturated starting material occurs when the subject process is used. Not only does this condition result in an improved yield of hydroxyiated product but the product may be isolated from the reaction mixture without encountering difficulties due to emulsification. Another factor which is advantageous is the fact that in using the subject process there is substantially no tendency for migration of the double bond(s) of-the unsaturated material prior to hydroxylation. Such action is characteristic of several of the prior art processes and is responsible to some extent for the low yields of desired product. Where the phenomenon of double bond migration is encountered, the double boud(s) generally migrate 8 towards the carboxylgroup. Consequently, lactone formation often results. In the subiect process, there is no double bond migration noticeable, and hence no lactone formation.

An additional advantage of the subject process lies in the fact that hydroxylation proceeds more rapidly than for any other process known. Further, the process is easily controlled on a large scale and does not require special equipment since no great heat evolution problem exists and no solidification of reactants occurs. The reaction is economically advantageous since a rather inexpensive oxidant is used and the products can easily be recycled to regenerate the oxidant.

All parts and percentage figures in the specification and appended claims are by weight unless otherwise indicated.

What I claim and desire to protect by Letters Patent is:

1. A process for the hydroxylation of an ethylenically unsaturated organic compound selected from the group consisting of ethylenically unsaturated fatty acids, ethylenically unsaturated fatty alcohols, esters of said fatty acids and esters of said fatty alcohols which comprises reacting in liquid phase said unsaturated organic compound and an inorganic persulfate in the presence of a saturated monocarboiwlic acid of from 1 to 9 carbon atoms and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

2. 'A process for the hydroxylation of an ethylenically unsaturated organic compound selected from the group consisting of ethylenically unsaturated fatty acids, ethylenicslly unsaturated fatty alcohols, esters of said fatty acids and esters of said fatty alcohols which comprises reacting in liquid phase said unsaturated organic compound and an inorganic persulfate in the presence of a saturated monocarboxylic acid of from 1 to 9 carbon atoms and a mineral acid having a dissociation constant for the first hydrogen at 25 C.

above 1.86 10 and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

'3. A process for the hydroxylation of an ethylenically unsaturated organic compound selected from the group consisting of ethylenically unsaturated fatty acids, ethylenically unsaturated fatty alcohols, esters of said fatty acids and esters of said fatty alcohols which comprises reacting in liquid phase said unsaturated organic compound and an inorganic persulfate in the presence of a saturated monocarboxylic acid of from 1 to 9 carbon atoms, a mineral acid have a dissociation constant for the first hydrogen at 25 C. above 1.86 x 10- and water and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

4. A process for the hydroxylation of an ethylenically unsaturated organic compound selected from the group consisting of ethylenically unsaturated fatty acids, ethyienically unsaturated fatty alcohols, esters of said fatty acids and esters of said fatty alcohols which comprises reacting in liquid phase said unsaturated organic compound and an inorganic persulfate in the presence of a saturated monocarboxylic acid of from 1 to 9 carbon atoms, a mineral acid having a dissociation constant for the first hydrogen at 25 C. above 1.86 10 and water, said inorganic persulfate being employed in the amount of at least one mol per mol of the unsaturated organic compound,

said saturated monocarboxylic acid being employed in the amount of at least one mol per mol of unsaturated organic compound, and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

5. A process for the hydroxylation of an ethylenically unsaturated organic compound selected from the group consisting of ethylenlcally unsaturated fatty acids, ethylenically unsaturated fatty alcohols, esters of said fatty acids and esters of said fatty alcohols which comprises reacting in liquid phase said unsaturated organic compound and an inorganic persulfate in the presence of a saturated monocarboxylic acid of from 1 to 9 carbon atoms, a mineral acid having a dissociation constant for the first hydrogen at 25 C. above 1.86 10 and water, said inorganic persulfate being employed in the amount of at least one mol per mol of unsaturated organic compound, said saturated monocarboxylic acid being employed in the amount 01 from 4 to 60 mols per mol of unsaturated organic compound, said water being employed in the amount of from 100% to 500% by weight of the unsaturated organic compound, said mineral acid being employed in the amount of at least one chemical equivalent per chemical equivalent of the inorganic persulfate, and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

6. A process for the hydroxylation of an ethylenically'unsaturated fatty acid which comprises reacting in liquid phase said unsaturated fatty acid and an inorganic persulfate in the presence of a saturated monocarboxylic acid of from 1 to 9 carbon atoms, a mineral acid havin a dissociation constant for the first hydrogen at 25 C. above 1136x10 and water, said inorganic persulfate being employed in the amount of at least one mol per mol of unsaturated fatty acid, said saturated monocarboxylic acid being employed in the amount of from 4 to 60 mols per mol of unsaturated fatty acid, said water being employed in the amount of from 100% to 500% by weight of the unsaturated fatty acid, said mineral acid being employed in the amount of at least one chemical equivalent per chemical equivalent of the inorganic persulfate, and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

'7. A process for the hydroxylation of oleic acid which comprises reacting in liquid phase said oleic acid and an inorganic persuliate in the presence of a saturated monocarboxylic acid of from 1 to 9 carbon atoms, a mineral acid having a dissociation constant for the first hydrogen at 25 C. above 1.86 10- and water, said inorganic persulfate being employed in the amount of at least one mol per mol of oleic acid, said saturated monocarboxylic acid being employed in the amount of from 4 to 60 mols per mol of oleic acid, said water being employed in the amount of from 100% to 500% by weight of the oleic acid, said mineral acid being employed in the amount of at least one chemical equivalent per chemical equivalent of the inorganic persulfate, and hydrolyzing the product to convert any ester groups resultin from the reaction to hydroxyl groups.

8. A process for the hydroxylation of oleic acid which comprises reacting in liquid phase said oleic acid and an inorganic persulfate in the presence of acetic acid, a mineral acid having a dissociation constant for the first hydrogen at 25 C. a-bove 1.86 10- and water, said inorganic persulfate being employed in the amount oi, at least one mol per mol of oleic acid, said acetic acid being employedin the amount of from 4 to 60 mols per mol of oleic acid, said water being employed in the amount of from 100% to 500% by weight of oleic acid, said mineral acid being employed in .the amount of at least one chemical equivalent per chemical equivalent of the inorganic persulfate, and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

9. A process for the hydroxylation of oleic acid which comprises reactin in liquid phase said oleic acid and an inorganic persulfate in the presence of acetic acid, sulfuric acid and water, said inorganic persulfate being employed in the amount of at least one mol per mol of oleic acid, said acetic acid being employed in the amount of from 4 to 60 mols per mol of oleic acid, said water being employed in the amount of from l 100% to 500% by weight of oleic acid, said sulfuric acid being employed in the amount of at least one chemical equivalent per chemical equivalent of the inorganic persuliate, and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

10. A process for the hydroxylation of oleic acid which comprises reacting in liquid phase said oleic acid and ammonium persulfate in the presence oi. acetic acid, sulfuric acid and water, said ammonium persulfate being employed in the amount of at least one mol per mol of oleic acid, said acetic acid being employed in the amount of from 4 to 60 mols per mol of oleic acid, said water being employed in the amount of from to 500% by weight of oleic acid, said sulfuric acid being employed in the amount of at least one chemical equivalent per chemical equivalent of the ammonium persulfate, and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

11. A process for the hydroxylation of oleic acid which comprises reacting in liquid phase said oleic acid and an inorganic persulfate in the presence of a saturated monocarboxylic acid of from 1 to 9 carbon atoms, a mineral acid having a dissociation constant for the first hydrogen at 25 C. above 1.86X 10" and water, said inorganic persulfate being employed in the amount of at least one mol per mol of oleic acid, said saturated monocarboxylic acid being employed in the amount of at least one mol per mol of oleic acid, and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

12. A process for the hydroxylation of oleic acid which comprises reacting in liquid phase said oleic acid and an inorganic persulfate in the presence of acetic acid, a mineral acid having a dissociation constant for the first hydrogen at 25 C. above 1.86 X 10- and water, said inorangic persulfate being employed in the amount of at least one mol per mol of oleic acid, said acetic acid being employed in the amount of at least one mol per mol of oleic acid, and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

13. A process for the hydroxylation of oleic acid which comprises reacting in liquid phase said oleic acid and an inorganic persulfate in the presence of acetic acid, sulfuric acid and water, said inorganic pers'ulfate being employed in the amount or at least one mol per mol of oleic acid, said acetic acid being employed in the amount of at least one mol per mol of oleic acid, and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

14. A process for the hydroxylation of oleic acid ll which comprises reacting in liquid phase said oieic acid and ammonium persuliate in the presence of acetic acid, sulfuric acid and water, said ammonium persulfate being employed in the amount 01' at least one mol per mol of oieic acid, said acetic acid being employed in the amount of at least one moi per mol of oleic acid, and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

15. A process for the hydroxylation of an ethylenicaily unsaturated organic compound selected from the group consisting of ethylenically unsat- I urated fatty acids. ethylenically unsaturated fatty alcohols, esters of said fatty acids and esters of said fatty alcohols which comprises reacting in 15 liquid phase said unsaturated organic compound 12 and an inorganic persultate in the presence at a saturated monocarboxylic acid 01 from 1 to 9 carbon atoms and water and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

16. A process for the hydroxylation of an ethylenically unsaturated fatty acid which comprises reacting in liquid phase said unsaturated fatty acid and an inorganic persulfate in the presence of a saturated monocarboxylic acid of from 1 to 9 carbon atoms and hydrolyzing the product to convert any ester groups resulting from the reaction to hydroxyl groups.

WALTER A. RACZYNSKI.

No references cited. 

1. A PROCESS FOR THE HYDROXYLATION OF AN ETHYLENICALLY UNSATURATED ORGANIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF ETHYLENICALLY UNSATURATED FATTY ACIDS, ETHYLENICALLY UNSATURATED FATTY ALCOHOLS, ESTERS OF SAID FATTY ACIDS AND ESTERS OF SAID FATTY ALCOHOLS WHICH COMPRISES REACTING IN LIQUID PHASE AND UNSATURATED ORGANIC COMPOUND AND AN INORGANIC PERSULFATE IN THE PRESENCE OF A SATURATED MONOCARBOXYLIC ACID OF FROM 1 TO 9 CARBON ATOMS AND HYDROLYZING THE PRODUCT TO CONVERT ANY ESTER GROUPS RESULTING FROM THE REACTION TO HYDROXYL GROUPS. 